Process for the preparation of chlor-substitution products of the saturated paraffin hydrocarbons.



UNITED ,sTA'r s PATENT OFFICE.

03mm .BLANG, or sxnon', on:

' invented new anduseful COMPANY, OF AIKR'OIIQI OHIO, A CORPORATION OF OHIO.

' Paoonss iron man rnnrans'rron' or cnnon-snnsr'rrurron rnonvcrs or ran fo all'qohoht it concern:

Be 1t. known that I, CHARLES Bianca l-"h. D., chemist, subject of Nicholas II,'Em-

peror'of'Russia, residin atAkron in the ate of Ohio, have.

county of Summit and Improvements in Processes for the Preparation of Chlor-Sfib stitution -Products.o f the Saturated Pareral formula CnH ydrocarbons, of which the following is a specificatiomi This invention relates to the production and manufacture, by direct chlorination, of

any specific individual chlorin derivative of a hydrocarbon ofthe parafiin, or methane series; the. hydrocarbon of the paraifin or methane series referred to havin the genmay be obtalned from or'asmineral or petroleum oils, or maybe procured fromany other source and byiany means whatsoever.

: Experience has shown that previous exproduetion only of-various mixtures of mono-, di-, tri, and higher chlorin substitution products, the separation of which is practically impossible and the chlor-d'erivatives o parai'fin v fby 'direct chlorination, it is impossible .to 86" proportions of each in the mixture being q ntrollable'.

'Beils tein Emma da- 1 ar ument]- Ohem'a'e 1893, volume 1, (page'142) states for example, that in the ro notion of the monohydrocarbons prevent the chlorination roceeding-too far, and the desirable mono-c obtained bya troublesome fractionation.

Meyer and Jacobson (Hanrlbuck der' 0rga/niscken Ohmic-1907, vol. 1, page 269) state:.-Finally oftheoretical interest is the formation of theQ'chloridsand bromide of i the parafiin hydrocarbons byfdirectsubsti place in liquid state, the substitution easily proceeds beyond the inonochlorid or monotuti'on. .Thisformatiomreaction cannot be. used as a method '0 f preparation because thechlorination or bromination does not give a pure product; the reaction takes romid to higher chloride or bromids.

"I have discoveredthat, by the use of some 7 reaction'favorin a ent's,- asany chemically act ve l ght an. be ogenscamer, employed of thee.

"to facilitate the reaction, chlorination of the hlgherparaflin' hydroorids can only be.

: tively cooling Specification of Letters Patent. 4 Patented Nofr, 27,1917. 7 ummies May 1, 1914. swi 835,620;

ample as mono,-, or di or tri-, or tetra-, or

any higher chlorin-substitution product of the employed paraifin hydrocarbon, such deslred specific; individual chlorinated ,par-

hydrocarbon, such for ex-" O, ABSIGNOR To THE GOODYEAR TIRE AND aflfin hydrocarbon being. substantially pure.

and free from other-undesirable, more or less-chlorinated products. Moreover, I am able toconduct. this direct ohlorination 'without the necessity of any preliminary change in the state of hydrocarbon; I

lorid.

e. chlorination in aggregation of the reacting am'also able to conduct this chlorination 'uponthe reacting hydrocarbon solvent,

by to control and order to secure any specific desired chlori- -nated'paraffin' hydrocarbon are as follows:

' Directly into'a mass of the employed paraflin hydrocarbon, contained in some suitable reaction chamber,- is conducted a stream of 'chlorin, in some measure regulated to conform with the quantity" of the hydrocarbon;

carbons, it-is advisable toadd tothe hydrocarbons some halogen-carrier. It is essen-v particularly in the tial to my process that the, reaction bhamher be provided with some means for efiecneously exposing said-contents to the daylight, or sunlight, or any chemically active artificial light. 4 i v The'contents of the reaction chamber are removed either continuously or intermittently, and any unchanged paraflin hydroits contents, and simultadistilling said unchanged par-- afiin hy rocarbon or undesirable lowe'r-" carbon or any undesirable lower-chlorinated chlorinated derivatives of the employs-d aflin 'hydrpcarbon being returned inany suitable manner to the reaction chamber where they are again submitted to the action of chlorin. The desired chlorinated paraflin hydrocarbon is removed from the still, washed with some aqueous alkaline solution, separated from the washing solution, and finally, if desired, dried and distilled.

To carry out my improved process and control and modify the course of chlorination in order to secure any specific desired chlorinated paraffin hydrocarbon, I make use of certain mechanical instrumentalities, a preferred form of which is shown in the accompanying drawing in which the same is illustrated diagrammatically, to which reference is hereby made.

It is to be understood that any changes, variations and modifications can be resorted to in connection with this process, which come within the scope of the matter hereinafter claimed.

In the drawing, the reference numeral 1 denotes a double tank or container constituting a reaction chamber, between the walls vof which is provided a space 2 in which is placed some cooling agent such for instance as cracked ice 3. In the side walls 4 of the member 1 are preferably placed some material transparent to the kind of light employed, such for instance, as glass or quartz, natural or artificial, may enter to the contents of the tank to the action and influence thereof. This light, as before mentioned, may consist of day light or any artificial light generated through the medium of electric lights 5 suitably placed for that purpose. The tank 1 is provided with an inlet pipe 6 provided with a cock 7 the opposite end of which is connected with a flask 8 containing a volume of water into which depends the discharge end of a ipe 9 connected with a tank 10' containmg chlorin. By this arrangement, the chlorin in the tank 10 passes into the flask 8 below the surface of the water and the chlorin bubbling up through the water attaches to itself a certain volume thereof, for I have found that the presence of moisture even in minute amounts is favorable to the conduct of the chlorination; the moist chlorin passes upwardly through the pipe 6, and disc arges into the tank 1 which constitutes the reaction chamber. The tank 1 is further provided with an inlet pipe 11 provided with a cook 12 and also provided near its upperend with a chamber 13 into which leads an inlet pipe 14' controlled by a cock 15- above which is a filling funnel 16. The chamber 1 is further provided with a con necting pipe 17 inwhlch is a cock 18, and

above the cock 18 is a series of coils 19 and 20 both of-which are surrounded by chambers 21 and 22 in which is placed cracked ice for a purpose to be later described. The upper end of'the pipe 17, after passing through flask 25 and terminating near the through which light, either subject.

Extending from the upper portion of the v bottom of a flask 28 is a pipe 29 having a cock 30. The flask 28 is partially filled with a volume. of naphtha 31. From the upper portion of the flask 28 leads a pipe 32 provided with a cook 33.

The reaction chamber is provided with an outlet 34 connecting near the lower portion thereof, the lower end of which terminates in a still 35. This pipe 34 is provided with a cock 36 and a drainage outlet 37 having a cook 38. Surrounding the still 35 and spaced therefrom, is a chamber 39 to receive a temperature-controlling medium trolling cook 44. In order to ascertain the temperature of the medium 40 surrounding the still 35 a thermometer 45 is provided. Extending upwardly from and having communication with the still 35 isa pipe 46-46, between the terminiof which is a chamber 47 surrounded by a casing 48 providing'a spherical space for a purpose to be later described. The upper portion of the pipe 46' is downwardly-bent at 49 and from thence is provided with a spirally-coiled portion 50 from which depends a pipe 51 terminating in the reaction chamber 1. This pipe 51 is provided with a cock 52. Surrounding the coiled portion 50 of the pipe 46 is a chamber 53 provided with an outlet 54 and an inlet 55. Connecting with the spherical space within the casing 48 is a T-tube 56 in which is mounted a thermometer 57 and this tube is provided at its lower end with a drainage pipe 58 provided with a cook 59. In open communication with the spherical space i'nclosed by the member 48 through the medium of a pipe 60, is a tank 61 provided near its lower end with an inlet 62. Extending in the tank 61 is a pipe 63 provided with an outlet -64 having a cock 65. This pipe 63 is provided in a tank61 with a plurality of spherically formed enlargements 66 and at its lower end with an inlet 67 having a cock 68.

Through #67 may be passed steam, hot water, cold water, or any other temperature controlling material the object ofthis mono-chlor-pentane from pentane.

I dgive a description of dllonsof pentane are introduced into a oulif' bottle of. 8 gallons ca acity by means of a funneL; Throu h anot .er upper 5 opening 1nthe Wou1fl vottle -a'.'stream of chlorin 1s introduced directly into'the dent that, my process may ,tirely continuous or intermittent, at; will.v The monorchlor-pentane accumulating n the still may be withdrawn as; desired, washed gentane. The Wou'lfi bottlerestsin an ice ath, which maintains the tem erature ofthe 'mterior of the-Wou-lif bott e at about 10 C.- "Cooling serves first tofnodi'fy the reaction by keeping downthe temperature 4 caused .by heat iberated duringthe chlorination, and-second to retain the entane in liquid form. The'Woulfi'bottle Wlth' its con-- 5 tents immersed-in an'ice bath, is exposed to the light of tung sten lamps. In.-place,-of,

ant material;- this chamber being provided 'W1th windows of I material which w satisfactorily transmit themstimulating chemically active rays of 1 a I Y i i nm' experimenting I have-found that, b 1n the ace oflight from the tungstenlamp',

.daylig t, sunlight, gas light, light from the ma'. successfully e "-electrlc'arc, the mercury vagor lamp, etc'.,

mpoye 11" order to further, encourage. the reac- 1 tion, I 'addto'the hydrocarbon, a halogencarr er, for. example,- 7 an aqueous solution of 'chloridof ron; however, the addition of:

the halogen-carrier is notalways necessa in the case .of the chlorination of the lower] 5 members of the paraflin hydrocarbon series;v

Furthermorathe chlorin bubbles through a water column "before it enters/the reaction chamber because I have found that the pres- -ence of moisture, even in. minute amounts, is favorable to'- .the conduct of the chlorination; also, this bubblin of chlorin through water enables. me :to o serve; and regulate the amount ofchlorin entering the reaction chamben. u After a few minutes the reaction s 4 this islindicated by the disappearance oi the ellfiow color-given to the reaction. mixture t are chlorin 1 is immediately reactive under. the,

describedaconditions, the reaction mixture,

remains colorless.-

vThe reaction mixture is withdrawn from thejreactionchamber into the still; the temperature of thestill content is,;in the .eas'e escribed, is

to a liquid paraflin namely, the preparation .Of"

QadditiOn 0 fresh pentan'eoulfi bottle for: a reaction chamber-I mayiuse a chamber of any resist-' lass, quartz -or .anyother he'trifling amount of chlorin dissolved;-

after, .becauseot the fact that the. added p h .w 10 than the chlor substitution product desired,

of penta'ne,'maintained atabout C. At t i this temperature the unchanged pentane. mixed wlth some of the desire mono-chlorpentane is vaporized and passes through the acketed tube which is kept at a temperature of-abou't 409 C., beinga few degrees above the boiling point of the entane, where further se aration takes p ace, the condensed mono-c lorid trickling back mto the still, and the unchanged. entane returning through a condenser, to t e'reaction' chamber for chlorination. A constantlevel ofreaction mixtureis maintained inthe reaction chamber b the continuous or intermlttent From this. foregoing description it is eviwithaqueou's solution of sodium carbonate, and if necessary,- dried and distilled.

I The hydrochloric acid gas evolved during the reaction passesofithrough a system of upright condensers, and thence. through a series of washin flasks, filled res 'ectively hydroc loric acid in armarketable form; in the -flask filled with alkaline solutiom the last'tracesof hydrochloric acid are removed-;

. I 'in the flaskfilled with naphtha, any pentane,

' mechanically carried over, 1 recovered. v .The process, conducted a% in the herein described example, ultimate y converts-all the employed pentane into ure monoi-ehlo'n' be either en'-' at I the, In ,the f pentane. In. order to pro. uce dichlor-pen'- tane, the rate ofipassage of the reaction mix;

ture through the apparatus is somewhat reduced over that suitable for the production of mono-chlor-pentane' the temperature of C. beinga tem eraturea jetween .theboiling point of dich or-pentane and the boiling point of the next ,lower chlor-pentane namely, monoschlor-pentane-.; wthe acketed tube is maintained at 108 In order to produce tri-,' or tetra. y. other d ired higher ohl i suitable temperature adjustments, ;an s

able control of rate of. passage. or the reacmo bon' material to' include not only t e liquid thestill contents is main ained at about no I a few digress above ,the boiling pointerthe monoc-or 11s arafiin-hydrocarbon itself, but also any i uid chlor-substitution is in a. lower stage. of chlorination Quilt: with or without a solvent therefor.

x-is

liquid paraflin-hydrocarbon material during product. thereof Y also obvious that when I obtain such recovered material may or may not be reintroduced into the process without in anywise altering this, my invention.,

I claim 1. A process for roducing a predeter mined chlor-substitutlon product ofa liquid paraffin-hydrocarbon, which consists in subjecting liquid paraflin hydroca'rbon material to the action of chlorin, actinic light, and

a temperature-regulating agent.

2. A process for producing a predetermined chlor-substitution product of a liquid parafiin-hydrocarbon, which comprises subjecting the hereinbefore defined liquid paraflin-hydrocarbon material to the simultaneous action of'chlorin, actinic light and a temperature-regulating agent.

3. A process for producing a predetermined chlor-substitution product of a liquid parafiin-hydrocarbon, which comprises, subjecting the hereinbefore defined liquid paraflin-hydrocarbon material to the simultaneous action of chlorin, actinic light, atemperature-regul'ating agent andachlorin car- 4. A process for producing a predetermined chlor-substitution productof a liquid paraffin-hydrocarbon, WhlCh comprises, 'subjecting the hereinbefore defined liquid-pan afiin-hydi'ocarbon material to the simultane ous action of ch10rin,.aetinic light and a temperature-regulatin agent, removing the desired chlor-substitution product, and adding a fresh supply of chlorin and the hereinbefore defined liquid parafli'n-hydrocarbon material to that material from which the chlor-substitution product was separated. I

In testimony whereof I. have hereuntoset my hand in presence of two subscribing witnesses. I

. CHARLES BLANG. Witnesses: A

C. E. HUMPHREY, A. L. MGOLIN'rooK. 

